This work demonstrates the ability of N,N-dimethylformamide + potassium thiocyanate(DMF + KSCN) to act as a novel complex solvent for the removal of benzene from its mixture with cyclohexane. The (liquid + liquid) equilibria (LLE) were measured for a quaternary system of (DMF + KSCN + benzene + cyclohexane) under atmospheric pressure and at temperature 298.15 K. The tie-line data for quaternary mixtures of (DMF + KSCN + benzene + cyclohexane) are also presented. The selectivity coefficients from these LLE data were calculated and found to be better than those previously reported in the literature for the (DMF + benzene + cyclohexane) systems. Excellent correlation of data by the nonrandom two-liquid (NRTL) model was seen for the quaternary system and the predicted results were found to be in fairly good agreement with experimental data. (C) 2014 Elsevier B.V. All rights reserved.